Unsaturated quaternary alkylated fatty acids and derivatives

ABSTRACT

ALIPHATIC QUATERNARY ALKYL COMPOUNDS HAVING UNSATURATION AT C-2,3, C-4,5 AND OR C-8,9 AND INTERMEDIATES THEREFOR USEFUL AS INSECT CONTROL AGENTS, LUBRICANTS, PLASTICIZERS AND ODORANTS.

United States Patent UNSATURATED QUATERNARY ALKYLATED FATTY ACIDS ANDDERIVATIVES Clive A. Henrick and John B. Siddall, Palo Alto, Calif.,assignors to Zoecon Corporation, Palo Alto, Calif. No Drawing. FiledSept. 28, 1970, Ser. No. 76,280

Int. Cl. C07c 69/52; A0111 9/24 US. Cl. 260-4103 R 13 Claims ABSTRACT OFTHE DISCLOSURE Aliphatic quaternary alkyl compounds having unsaturationat C-2,3, C-4,5 and/or C-8,9 and intermediates therefor useful as insectcontrol agents, lubricants, plasticizers and odorants.

This invention relates to novel unsaturated quaternary alkyl compounds,intermediates therefor, syntheses thereof and the control of insects.

The novel unsaturated quaternary alkyl esters of the present inventionand derivatives thereof are represented by the following formulas:

wherein, R is lower alkyl and R is hydrogen, alkyl, cycloalkyl, aralkyl,aryl or a metal.

The term alky, as used herein, refers to a straight or branched chainsaturated aliphatic hydrocarbon group having a chain length of one toeight carbon atoms. The term lower alkyl, as used herein, refers to aprimary or secondary alkyl group having a chain length of one to sixcarbon atoms. The term cycloalkyl, as used herein, refers to acycloalkyl group of four to eight carbon atoms. The term aralkyl, asused herein, refers to an aralkyl group of seven to twelve carbon atoms,such as benzyl, phenylethyl, methylbenzyl and naphthylmethyl. The termaryl, as used herein, refers to an aryl group of six to twelve carbonatoms, such as phenyl, methylphenyl, naphthyl, and the like. The termmetal, as used herein, refers to lithium, sodium, potassium, calcium,strontium, copper and manganese.

The compounds of Formulas A, B and C are useful for the control ofinsects. The utility of these compounds as insect control agents isbelieved to be attributable to their juvenile hormone activity. They arepreferably applied to the immature insect, namely-during the embryo,larvae or pupae stage in view of their ability to inhibit metamorphosisand otherwise cause abnormal development. These compounds are effectivecontrol agents for Hemipteran insects, such as Lygaeidae, Miridae andPyrrhocoridae; Lepidopteran insects, such as Pyralidae, Noctuidae andGelechiidae; Coleopteran, such as Tenebrionidae; and Dipteran. Thecompounds can be applied at low dosage levels of the order of 0.001 g.to 15.0 g. per insect. Suitable carrier substances include liquid orsolid carriers, such as water, mineral or vegetable oils, talc,vermiculite, natural and synthetic resins and silica. Treatment3,712,922 Patented Jan. 23, 1973 of insects in accordance with thepresent invention is accomplished by spraying dusting or exposing theinsects to the vapor of the compounds of Formulas A, B and C. Generally,a concentration of less than 25 of the active compound is employed. Theformulations can include insect attractants, emulsifying agents orWetting agents to assist in the application and effectiveness of theactive ingredient. In the application of the compounds, there isgenerally employed a mixture of the C-2,3 trans and cis isomers, the02,3 trans isomer being the preferred embodiment for the control ofinsects.

In the description following and hereinafter, each of R and R is definedas hereinabove and R is alkyl, cycloalkyl, aryl or aralkyl.

The compounds of the present invention are prepared according to thefollowing outline syntheses.

The novel triene esters (A') are prepared by the reaction of thealdehyde (IV) with the carbanion of the Formula VIII:

The phosphonate anion (VIII) is generated by treatment of thecorresponding phosphonate with base, such as alkali metal hydride oralkali :metal alkoxide, e.g. sodium hydride or sodium methoxide, inorganic solvent inert to the reaction, such as a hydrocarbon, ether ordialkylsulfoxide solvent, e.g. benzene, toluene, dimethylformamide,tetrahydrofuran, and the like. The reaction is conducted at atemperature of from about 20 C. to room temperature or above. Thereaction of the phosphonate anion with the aldehyde is generallyconducted at temperature of about 0? C. to room temperature or above.The phosphonate can be prepared as described by Pattenden et al., J.Chem. Soc. (C), 1984 and 1997 (1968). The esters (A') are converted intothe corresponding acid (A; R is hydrogen) by hydrolysis with base, suchas potassium carbonate or sodium carbonate in organic solvent, such asmethanol or ethanol. Other esters of the present invention can beprepared by transesterification or conversion of the acid into the acidhalide by treatment with thionyl chloride, oxalyl chloride, or the like,and then reacting the acid halide with the alcohol corresponding to theester moiety desired.

In the preparation of the diene esters of formula B, an aldehyde ofFormula IV is hydrogenated using palladium on charcoal or other catalystto yield the saturated aldehyde (V) which is reacted with phosphonateanion of Formula IX using the conditions described above or with an ylidof Formula X to yield the unsaturated ketone (VI).

Conversion of VI into B using phosphonate anion can be done using thesame conditions as for conversion of IV into A: Wittig reactions aregenerally done at higher temperatures, such as from room temperature toreflux. The ylids are prepared from the corresponding phosphoniumbromide or chloride by treatment with a base, such as butyl lithium,alkali metal hydride, alkali metal hydroxide or alkali metal carbonatein an organic solvent, such as toluene, benzene, or tetrahydrofuran, orwater or aqueous organic solvent depending upon the particular base.

In the preparation of the diene esters of Formula C, an aldehyde ofFormula IV is reacted with a phosphonate anion (IX) or ylid (X) toobtain the di-unsaturated ketone (V) which is hydrogenated selectivelyusing palladium in basic medium, lithium and liquid ammonia, or thelike, to yield the corresponding 3,4-dihydro ketone (VII). Suitablehydrogenation procedures are described by Augustine, CatalyticHydrogenation, M. Dekker, New York, pages 60-62 (1965); Augustine,Reduction, M. Dekker, New York, pages 104-105 (1968) and House, ModernSynthetic Reactions, W. A. Benjamin, Inc., New York, pages 61-66 (1965).The ketone (VII) is then converted into an ester of formula C byreaction with a phosphonate anion of Formula XI or an ylid of FormulaXII. The esters B and C can be hydrolyzed using base to obtain acids ofFormulas B and C wherein R is hydrogen.

The aldehydes of Formula IV are prepared according to H CH (III) Theketone (I), prepared by the alkylation of phorone using an organo-coppercomplex prepared from lower alkyl lithium or lower alkyl magnesiumhalide and cuprous iodide, is reduced using lithium aluminum hydride orsodium borohydride to yield the alcohol (II). See Anderson et al., J.Amer. Chem. Soc. 92, 735 (1970) and Siddall et al., J. Amer. Chem. Soc.91, 1853 (1969). The alcohol (11) is then reacted with a lower alkylvinyl ether in the presence of mercuric acetate to yield the vinyl ether(III) which upon heating, under inert atmosphere, at a temperature ofabout C. to about 220 C., generally 180 C. to 210 C., in a sealed vesselyields the unsaturated aldehyde (IV).

The compounds of Formulas IV, V, VI and VII, in addition to theirutility as intermediates for the insect control agents of Formulas A, Band C, are useful in chemical syntheses in general, such as thepreparation of perfumery additives and as odorants for perfumerycompositions. The polyene esters of Formulas A, B and C are usefullubricants and plasticizers for polymers, such as hydrocarbon polymersand chlorinated hydrocarbon polymers.

The following examples are provided to illustrate the present invention.Temperature is given in degrees centigrade.

EXAMPLE 1 (A) To a suspension of cuprous iodide (25 g.) in 500 ml. ofdry ether at 0 is added 150 ml. of 1.6 M methyl lithium in ether at amoderate rate with stirring under argon. After about 20 minutes at 0, 14g. of phorone in 30 ml. of ether is added slowly and the mixture stirredfor about 0.5 hour. The mixture is then poured into rapidly stirredaqueous ammonium chloride (about one liter), allowed to stand and thelayers separated. The ether layer is washed with saturated sodiumchloride, the water layer is extracted with ether and combined with theether phase and dried over sodium sulfate and filtered. The filtrate isevaporated in vacuo to yield 2,6,6-trimethylhept-2-en-4-one.

(B) 100 grams of ketone of Part A dissolved in a mixture of 100 ml. ofanhydrous ether and 100 ml. of hexane is added dropwise to a suspensionof 10 g. lithium aluminum hydride in 500 ml. anhydrous ether at 0. Themixture is stirred for 90 minutes at 0, quenched by dropwise addition ofwater and extracted with ether. The extract is washed with brine anddried. Evaporation of the solvent and distillation of the residue gives2,6,6- trimethylhept-2-en-4-ol.

(C) 67 grams of alcohol of Part B and 12 g. mercuric acetate (freshlyrecrystallized from ethanol containing 1% acetic acid) are dissolved in600 ml. of ethyl vinyl ether and refluxed for eight hours. Another 12 g.mercuric acetate is added and the solution further refluxed overnight.The solution is cooled to 0 and 200 ml. of saturated potassium carbonateis added. After one hour stirring, the organic layer is separated andwashed with brine. After evaporation of the solvent, the vinylether(III; R is methyl) is heated in a bomb under nitrogen for one hour at-210. After cooling to room temperature, the reaction product isfiltered in hexane through a short column of Woelm neutral alumina (activity III) and distilled to yield 3,3,7,7-tetramethyloct-4- en-l-al.

(D) The process of Part A is repeated using each of ethyllithium,n-propylithium, i-propylithium and butyllithium in place ofmethyllithium to yield 2,6,6trimethyl oct-2-en-4-one,2,6,6-trimethylnon-2 en 4 one, 2,6,6,7- tetramethyloct-Z-en-4-one and2,6,6-trimethyldec-2-en-4- one, respectively, which are reducedaccording to the procedure of Part B to the corresponding C-4 alcohol ofFormula II. Each of the thus-obtained alcohols is reacted with ethylvinyl ether using the procedure of Part C above to yield thecorresponding vinyl ether of Formula III (R is ethyl, n-propyl, i-propyland n-butyl, respectively). The vinyl ethers are heated using theprocedure of Part C above to yield the corresponding aldehyde, that is3,3,7,7-tetramethylnon-4-en-l-al, 3,3,7,7-tetramethyldec 4 en l a1,3,3,7,7,8pentamethylnon-4-en- 1-al and 3,3,7,7 tetramethylundec 4 en 1al, respectively. Similarly, using n-hexyl lithium in place of methyllithium, there is obtained, as the final product, 3,3,7,7-tetramethyltridec-4-en 1 al, by the processes of this example.

EXAMPLE 2 Sodium methoxide (from 200 mg. sodium and 12 ml. methanol) isadded dropwise to a stirred solution of 1.8 g. of trans diethyl3ethoxycarbonyl-2-methylprop2-enyl phosphonate (VIII; R=R =ethyl) and 1g. of 3,3,7,7- tetramethyloctl-en-l-al in 50 ml. of dimethylformamideunder nitrogen. The reaction mixture is left for one hour at roomtemperature and then water is added followed by extraction with ether.The ethereal extracts are Washed with brine, dried and evaporated toyield trans/cis methyl 3,7,7,l1,l1-pentamethyldodeca-2,4,8 trienoate.The isomeric mixture can be chromatographed on silica or distilled forpurification. The I isomeric mixture is predominantly trans at C-2,3.

The foregoing procedure is repeated using sodium ethoxide in place ofsodium methoxide to yield trans/ cis ethyl3,7,7,11,1l-pentamethyldodeca-2,4,8-trienoate.

The procedure of this example is repeated using sodium ethoxide in placeof sodium methoxide and using each of the aldehydes of Example 1 (PartD) in place of 3,3,7,7-tetramethyloct-4-en-1-al to yield trans/cis ethyl3,7,7,11,11-pentamethyltrideca-2,4,8 trienoate, trans/cis ethyl3,7,7,11,1l-pentamethyltetradeca 2,4,8 trienoate, trans/cis ethyl3,7,7,11,l1,l2-hexamethyltridec-2,4,8-trienoate, trans/cis ethyl3,7,7,11,1l-pentamethylpentadeca- 2,4,8-trienoate and trans/cis ethyl3,7,7,11,ll-penta methylheptadeca-2,4,8-trienoate, respectively.Similarly, the corresponding methyl esters are prepared from thealdehydes of Example 1(D) using the process of this example. Thetrans/cis isomeric mixture of each of the foregoing compounds isseparable into the individual isomers using gas-liquid chromatography orfractional distillation.

EXAMPLE 3 To a mixture of 250 mg. of sodium hydride in 2 ml. oftetrahydrofuran, with ice-cooling, is added 1.6 g. of trans diethyl3-ethoxycarbonyI-Z-methylprop-Z-enyl phosphonate in 5 ml. oftetrahydrofuran. Temperature is allowed to rise to room temperature andafter 30 minutes, 1 g. of 3,3,7,7-tetramethyloct-4-en-l-al is added.After about one hour at room temperature, the mixture is extracted withether. The ethereal extracts are washed with brine, dried and evaporatedto yield trans/cis ethyl 3,7,7,11,l1-pentamethyldodeca-2,4,8-trienoate(about 1:1 mixture of C-2,3 trans and cis isomers).

EXAMPLE 4 Two grams of 3,3,7,7,-tetramethyloct-4en-l-al in ml. ofethanol over 100 mg. of 5% palladium-on-ch-arcoal is hydrogenatedovernight. The catalyst is filtered to yield3,3,7,7-tetramethyloctan-l-al.

EXAMPLE 5 (A) One gram of 5% palladium-on-carbon and 10 g. of3,3,7,7-tetramethyloct-4-en-l-al is stirred in 50 ml. of ethanol underexcess hydrogen at one atmosphere pressure and at room temperature untilthe theoretical amount of hydrogen is absorbed (about 48 hours). Then, 2ml. of dichloromethane is added and the mixture filtered. The filtrateis concentrated under reduced pressure to yield3,3,7,7-tetramethyloctan-l-al.

By use of the foregoing procedure, each of the aldehydes of Example 1(D)is hydrogenated to the corresponding 4,5-dihydro compound.

(B) To 126 mg. of a 57% dispersion of sodium hydride in oil is addedpentane. The pentane is removed and the sodium hydride washed severaltimes with pentane. To the washed sodium hydride is added 582 mg. ofdiethyl acetylmethylphosphonate (IX; R is ethyl) in 5 ml. oftetrahydrofuran at 10 under argon. After several minutes, the solutionis transferred to a solution of 500 mg. of 3,3,7,7-tetramethyloctan-l-alin about 4 ml. of dry tetrahydrofuran under argon over a period of about20 minutes at room temperature. After about two hours, water is addedfollowed by addition of ether and the layers separated. The organiclayer is washed with saturated sodium chloride, dried over sodiumsulfate and evaporated under reduced pressure to yield6,6,10,10-tetramethylundec-Ii-en-Z-one.

Similarly, each of 3,3,7,7-tetramethylnonan-l-al, 3,3,7,7-tetramethyldecan-l-al, 3,3,7,7,8-pentamethylnonan 1- al,3,3,7,7-tetramethylundecan-l-al and 3,3,7,7-tetramethyltridecan-l-al isconverted into- 6,6,10,10-tetramethyldodec-3-en-2-one,6,6,10,10-tetramethyltridec-3-en-2-one,6,6,l0,l0,1l-pentamethyldodec-3-en 2 one, 6,6,10,10-tetramethyltetradec-3-en-2-one and6,6,10,10-tetramethylhexadec-3-en-2-one, respectively.

By use of the process of this example, other Z-ketones of Formula VI areprepared.

(C) 32.2 grams of sodium hydride (57% in oil) is placed in a dry 1:1,3-neck flask (fitted with a nitrogen inlet) and Washed three times ml.each) With dry pentane under nitrogen, carefully decanting only thesolvent each time, into a beaker of ethanol. 400 milliliters drytetrahydrofuran is then added, the mixture cooled to 0, and 156.0 g. ofdiethyl carbethoxymethylphosphonate (XI; R=R '=ethyl) is added undernitrogen. The solution is stirred for 0.5 hour after addition iscomplete, and then 123.5 g. of 6,6,10,10-tetramethylundec-3-en-2-one in250 ml. dry tetrahydrofuran over 0.5 hour period at room temperatureunder nitrogen. The mixture is stirred overnight and then poured intosaturated NaCl at 0 and extracted with ether (3X 200 ml.), the organiclayers dried (CaSO and concentrated under reduced pressure to yieldtrans/cis ethyl 3,7,7,l1,1l-pentamethyldodeca-2,4- dienoate which can beseparated into the individual C-2,3 trans and cis isomers usinggas-liquid chromatography or fractional distillation.

The above process is repeated using each of the 2- ketones of Part B asthe starting material to yield trans/ cis ethyl 3,7,7,1l,11pentamethyltrideca 2,4 dienoate, trans/cis ethyl 3,7,7,11,11pentamethyltetradeca 2,4- dienoate, trans/cis ethyl 3,7,7,11,l1hexamethyltrideca- 2,4 dienoate, trans/cis ethyl 3,7,7,11,11pentamethylpentadeca 2,4 dienoate and trans/cis ethyl3,7,7,ll,1lpentamethylheptadeca-2,4-dienoate, respectively.

By using diethyl carbomethoxymethylphosphonate in the process of Part C,the corresponding 2,4-diene methyl esters are obtained. Similarly, byuse of the processes of this example, other esters of Formula B areobtained.

EXAMPLE 6 (A) The process of Example 5(B) is repeated with the exceptionof using 3,3,7,7 tetramethyloct-4-en-l-al in place of 3,3,7,7tetramethyloctan l al to yield 6,6,10, l0 tetramethylundeca 3,7 diene 2one. Similarly, each of the mono-unsaturated aldehydes of Example 1(D)are converted into the corresponding di-unsaturated 2- ketones ofFormula V, i.e. 6,6,10,10-tetramethyldodeca- 3,7 dien 2 one,6,6,10,10-tetramethyltrideca-3,7-dien- 2-one,6,6,10,10,1l-pentamethyldodeca 3,7 dien-Z-one, 6,6,10,10tetramethyltetradeca 3,7 dien 2 one and 6,6,10,10 tetramethylhexadeca3,7 dien 2 one, respectively.

(B) Each of the di-unsaturated ketones of Part A is reduced usinglithium in liquid ammonia to yield the corresponding 3,4-dihydrocompound of Formula VII, that is 6,6,10,10 tetramethylundec-7-en-2-one,6,6,10,10- tetramethyldodec 7 en 2 one,6,6,10,10-tetramethyltridec-7-en-2-one, 6 ,6 ,l0,10,11pentamethyldodec-7-en-Z- one, 6,6,l0,10-tetramethyltetradec-7-en-2-oneand 6,6, 10,10-tetramethylhexadec-7-en-2-one, respectively.

(C) The 2-ketones of Part B are used as the starting material in theprocess of Example 5 (C) to yield the corresponding diene esters ofFormula C, that is, trans/ cis ethyl 3,7,7,11,11 pentamethyldodeca 2,8dienoate, trans/cis ethyl 3,7,7,l1,l1 pentamethyltrideca-Z,8-dienoate,trans/cis ethyl 3,7,7,11,ll pentamethyltetradeca-Z,8-

dienoate, trans/cis ethyl 3,7,7,11,11,l2 hexamethyltrideca 2,8 dienoate,trans/cis ethyl 3,7,7,11,11 pentamethylpentadeca 2,8 dienoate andtrans/cis ethyl 3,7, 7,11,11 pentamethylheptadeca 2,8 dienoate,respectively. The individual C-2,3 trans and cis isomers can beseparated by gas-liquid chromatography or fractional distillation. Thecorresponding methyl esters are obtained using the diethyl phosphonateanion of Formula XI wherein R is methyl.

EXAMPLE 7 A mixture of 1 g. of trans/cis methyl3,7,7,ll,1lpentamethyldodeca-2,4,8-trienoate, 60 ml. of methanol, 0.2 g.of sodium carbonate and 6 ml. of water is stirred at about 30 for about24 hours. The mixture is then diluted with water, neutralized andextracted with ether. The organic phase is washed with water, dried oversodium sulfate and evaporated to yield trans/cis 3,7,7,11,11-pentamethyldodeca-2,4,8-trienoic acid.

Using the foregoing procedure, the other esters of Formulas A, B and Care hydrolyzed to the corresponding free acid.

EXAMPLE 8 One gram of thionyl chloride is added with stirring at roomtemperature to 0.5 g. of trans/cis 3,7,7,11,11-pentamethyldodeca-2,4,8-trienoic acid and the mixture heated at about 50for 10 minutes. Excess thionyl chloride is removed by evaporation andthen t-butyl alcohol (about 2 equivalents) is added and the mixtureheated at about 50 for about five minutes. Excess t-butyl alcohol isremoved by evaporation to yield trans/cis t-butyl 3,7,7, 11,11pentamethyldodeca 2,4,8 trienoate which is purified by chromatography.

Similarly, by using other alcohols, such as cyclohexyl alcohol, benzylalcohol, phenol, n-pentanol, n-hexyl alcohol or i-propanol in theforegoing procedure, the corresponding esters are obtained.

EXAMPLE 9 To a solution of 0.5 g. of trans/cis3,7,7,11,11-pentamethyldodeca 2,4,8 trienoic acid in 15 ml. of benzeneis added with stirring an equivalent amount of potassium bicarbonate.The mixture is stirred until the evolution of carbon dioxide ceases andthen evaporated to yield potassium 3,7 ,7,11,11-pentamethyldodeca-2,4,8-trienoate.

Alternatively, acid salts can be prepared by titrating the acid with anorganic solution or aqueous organic solution of the desired metal.

EXAMPLE 10 To 1.6 g. of sodium hydride (57% in oil dispersion) in a 500ml., 3-neck flask, fitted with a nitrogen inlet, is added 25 to 50 ml.of dry hexane or pentane and the mixture swirled under nitrogen. The NaHis allowed to settle and the solvent carefully decanted into a beakercontaining ethanol. This rinsing process is repeated twice and 100 m1.dry tetrahydrofuran is added via syringe or pipet. Mixture is cooled inan ice-bath and 9.0 g. triethyl phosphonoacetate (dried over molecularsieves) is added via additional funnel over a 10 minute period. Stir anadditional one-half hour. The solution of the above anion is transferredvia syringe to a 125 ml. addition funnel (with pressure equalizing arm)and is added over about one hour to 6.73 g. of 6,6,10,10tetramethyldodec-7-en- 2-one at room temperature with stirring. Thehomogenous solution is then stirred overnight (1824 hours). The mixtureis then poured into saturated sodium chloride at and extracted withether. The organic phase is dried and concentrated under reducedpressure to yield trans/ cis ethyl 3,7,7,11,11 pentamethyltrideca 2,8dienoate which can be purified by chromatography or distillation.

EXAMPLE ll 41 grams of 3,3,7,7-tetramethyloct-4-en-l-al and 78.4 g. ofrecrystallized (ethyl acetate) triphenylphosphincacetylmethylene[Ramirez et al., J. Org. Chem. 22, 41 (1957)] are refluxed in one literof dry toluene for 18 hours, under nitrogen. Most of the solvent isremoved in vacuo, 500 ml. pentane is added and the mixture filtered. Theflask and the triphenylphosphine oxide filter cake are washed severaltimes with pentane. The filtrate is concentrated in vacuo to yield6,6,10,lO-tetramethylundeca-3,7-dien-2-one.

By use of the foregoing Wittig reaction, other aldehydes of Formula IVare converted into the corresponding di-unsaturated Z-ketones of FormulaVII.

EXAMPLE 12 One gram of triphenylphosphine acetylmethylene and 450 mg. of3,3,7,7-tetramethylnon-4-en-l-al are dissolved in 10 ml. toluene andrefluxed under nitrogen overnight. The toluene is distilled off and theformed triphenylphosphine oxide crystallized by addition of pentane.Filtration and evaporation of the pentane gives a residue, which isfurther purified by preparative thin-layer chromatography, with theplate eluted with 15% ethyl acetatezhexane. Removal of the UV activeband gives 6,6,10,10-tetramethyl dodeca-3,7-dien-2-one.

EXAMPLE 13 One gram of 6,6,10,10-tetramethylundeca-3,7-dien-2- one in 10ml. of 0.3 N potassium hydroxidezethanol over mg. of 5%palladium-on-charcoal is hydrogenated at room temperature andatmospheric pressure, until the theoretical amount of hydrogen is takenup, to yield 6,6,10,lO-tetramethylundec-7-en-2-one which is worked up byfiltration followed by evaporation under reduced pressure.

EXAMPLE 14 The diene esters (B') can be prepared in one step from thesaturated aldehydes (V) by reaction with the phosphonate anions (VIII)using the conditions described herein for conversion of aldehyde IV tothe esters A.

What is claimed is:

1. A compound selected from those of the following formulas:

wherein, R is lower alkyl and R is hydrogen, lower alkyl, cycloalkyl,aryl, aralkyl or a metal.

2. A compound according to claim 1 wherein the configuration at C-2,3 istrans/cis.

3. A compound according to claim 2 wherein R is lower alkyl.

4. A compound of Formula A according to claim 2.

5. A compound according to claim 4 wherein R is lower alkyl and R ismethyl, ethyl or propyl.

6. A compound according to claim 5 wherein each of R and R is methyl orethyl.

7. A compound of Formula B according to claim 2.

10 8. A compound according to claim 7 wherein R is meth- ReferencesCited y ethyl or p py and R1 is lower y UNITED STATES PATENTS 9. Acompound according to claim 8 wherein each of 3,177,226 4/1965 still eta1 R and R is methyl or ethyl. 5 OTHER REFERENCES 10. A compound ofFormula C according to claim 2. I 11. A compound according to claim 10wherein R is ChemlcalAbstmcts VOL 95597r (1968) methyl, ethyl or propyland R is lower alkyl. LEWIS GOTIS, Primary Examiner 12. A compoundaccording to claim 11 wherein each 10 G RIVERS7 Assistant Examiner of Rand R is methyl or ethyl.

13. A compound according to claim 2 wherein R is CL hydrogen, loweralkyl of one to four carbons, benzyl, cy- 4110, 593 clopentyl orcyclohexyl. 601 R, 606.5 F, 614 R, 941; 424312, 315.

